[go: up one dir, main page]

EP0436944A2 - Epoxy resin composition for fiber reinforced plastic - Google Patents

Epoxy resin composition for fiber reinforced plastic Download PDF

Info

Publication number
EP0436944A2
EP0436944A2 EP90125692A EP90125692A EP0436944A2 EP 0436944 A2 EP0436944 A2 EP 0436944A2 EP 90125692 A EP90125692 A EP 90125692A EP 90125692 A EP90125692 A EP 90125692A EP 0436944 A2 EP0436944 A2 EP 0436944A2
Authority
EP
European Patent Office
Prior art keywords
component
resin composition
weight
parts
epoxy resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90125692A
Other languages
German (de)
French (fr)
Other versions
EP0436944B1 (en
EP0436944A3 (en
Inventor
Seiichi Hino
Jun Enda
Masaki Yamamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp, Mitsubishi Kasei Corp filed Critical Mitsubishi Chemical Corp
Publication of EP0436944A2 publication Critical patent/EP0436944A2/en
Publication of EP0436944A3 publication Critical patent/EP0436944A3/en
Application granted granted Critical
Publication of EP0436944B1 publication Critical patent/EP0436944B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to a resin composition for fiber reinforced plastic. More particularly, it relates to a resin composition suitable for fiber reinforced plastic materials wherein fibers of high elasticity are employed.
  • the prepreg has a proper adhesiveness (tackiness) so that prepreg sheets adhere to one another at the time of laying up, and a flexibility (draping properties) so that laid up prepreg layers accurately reflect the shape such as a curved surface or cylinder.
  • adhesiveness tackiness
  • flexibility draping properties
  • thermosetting molding by blending a phenol novolak type epoxy resin to such as resin composition, a molded product having no internal voids after the thermosetting molding can be obtained while adequately maintaining the shape-maintaining strength of the prepreg sheets and excellent draping properties (Japanese Patent Application No. 170228/1988).
  • Such a resin composition does not create any particular problem when applied to fiber reinforced plastic materials wherein reinforcing fibers of usual physical properties are employed.
  • the reinforcing fibers have a high modulus of elasticity, the tackiness tends to be slightly poor, and it frequently happens that the shape after the shape-forming can not be maintained.
  • the present inventors have conducted extensive researchs to solve such a problem and as a result have found that the tackiness can be improved by using a combination of two bisphenol A type epoxy resins having specific physical properties and being solid at room temperature, as the high molecular weight components, whereby the conventional problems can be solved, and a resin composition having balanced properties can be obtained.
  • the present invention has been accomplished on the basis of this discovery.
  • an epoxy resin composition for fiber reinforced plastic comprising the following components A, B, C, D, E and F as essential components and having a viscosity at 40°C of at least 10,000 poise and a viscosity at 80°C of at most 200 poise:
  • component A having an epoxy equivalent of at most 250 and being liquid at room temperature
  • component A having an epoxy equivalent of at most 250 and being liquid at room temperature
  • any such compound may be used so long as it has an epoxy equivalent of at most 1,000, preferably from 400 to 1,000, and a softening point of at most 100°C, preferably from 60 to 100°C.
  • the following compounds may be mentioned: "EPOKOTE” 1001, 1002, 1004, manufactured by Yuka Shell Epoxy Company, "D. E.
  • any such compound may be used so long as it has an epoxy equivalent of at least 1,100, preferably from 1,100 to 5,000, more preferably from 1,100 to 3,500, and a softening point of at least 110°C, preferably from 110 to 200°C, more preferably from 110 to 160°C.
  • the following compounds may be mentioned: "EPIKOTE” 1007, 1009, 1010, manufactured by Yuka Shell Epoxy Company, "D. E.
  • the phenol novolak type epoxy compound (component D) means a compound of the formula: wherein n is an integer.
  • phenol novolak type epoxy resin component D
  • the following compounds may specifically be mentioned: "EPIKOTE” 152, 154, manufactured by Yuka Shell Epoxy Company, “Araldite” EPN1138, EPN1139, manufactured by Ciba Geigy Company, “D.E.N” 431, 438, 439, 485, manufactured by Daw Chemical Company, "EPPN” 201, manufactured by Nippon Kayaku K.K., "EPICRON” N-730, N-738, N-740, manufactured by Dai Nippon Ink Kagaku K.K.
  • the nitrile rubber of component E is not particularly restricted, and it is usual to employ the one having an average molecular weight of at least 10,000. Specifically, a copolymer of butadiene and acrylonitrile may be employed. Further, it may be a copolymer having acrylic acid added to butadiene and acrylonitrile. It is usual to employ such copolymer having an average molecular weight of about 50,000. The acrylonitrile content is usually from 15 to 40% by weight.
  • the nitrile rubber of component E may be incorporated independently in the form of nitrile rubber to the epoxy resin composition of the present invention. However, it is preferred to preliminarily mixing and reacting it with the epoxy compound of component A so that it may be incorporated in the form of a nitrile rubber-modified epoxy compound thus obtained.
  • the above mentioned respective components are essential components, and their proportions are preferably such that relative to 100 parts by weight of component A, component B is from 5 to 40 parts by weight, component C is from 5 to 40 parts by weight, component D is from 50 to 140 parts by weight and component E is from 1 to 8 parts by weight.
  • the resin composition of the present invention has a viscosity at 40°C ( ⁇ 40°C) of at least 10,000 poise, preferably from 10,000 to 40,000 poise, more preferably from 10,000 to 30,000 poise and a viscosity at 80°C ( ⁇ 80°C) of at most 200 poise, preferably from 20 to 200 poise, more preferably from 50 to 150 poise.
  • the viscosity ( ⁇ 40°C) is less than 10,000 poise, the surface tends to be sticky although the operation efficiency may be improved. On the other hand, if it is too high, the operation efficiency tends to be poor, since the hardness tends to be too high.
  • component A and components B and C primarily serve to adjust the viscosity of the resin composition.
  • the adhesive properties of the resin composition can be improved by the combined use of components B and C.
  • Component E serves primarily to impart excellent operation efficiency and is effective particularly for the improvement of the flexibility of the resin composition.
  • Component D serves to prevent formation of voids in the interior of the molded product. If components D and E are not incorporated, it tends to be difficult to impart good flexibility with a proper viscosity during the preparation of prepreg sheets or during the molding operation, and voids tend to form in the interior of the molded product, such being very inconvenient.
  • an aliphatic epoxy resin an o-cresol novolak type epoxy resin, a polyglycidyl amine, a bisphenol F type epoxy resin, a brominated bisphenol A type epoxy resin, 1,1,2,2-tetrabis(4-glycidoxyphenyl)ethane, a glycidyl ester type epoxy resin and a monofunctional epoxy compound, may further be incorporated, as the case requires.
  • the curing agent of component F may usually be any curing agent. It may be dicyandiamide, an acid anhydride, an aromatic diamine, dimercaptan or a phenol resin. Further, in order to impart storage stability and low temperature curability to the prepreg, it is effective to employ a combination of dicyandiamide and a curing accelerator. Even when dicyandiamide is used alone, no change is required in the operation prior to the molding, provided that the molding compositions such as the curing temperature may vary.
  • the curing accelerator may be an imidazole derivative such as 2-ethyl-4-methylimidazole or 2-(2-cyanoethyl)-imidazole, or a urea derivative such as N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethylurea or N-(3-chlorophenyl)-N',N'-dimethylurea.
  • an imidazole derivative such as 2-ethyl-4-methylimidazole or 2-(2-cyanoethyl)-imidazole
  • a urea derivative such as N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethylurea or N-(3-chlorophenyl)-N',N'-dimethylurea.
  • dicyandiamide a combination of dicyandiamide and a curing accelerator
  • dicyandiamine is incorporated in an amount of form 0.5 to 10 parts by weight, based on 100 parts by weight of the entire resin mixture
  • the curing accelerator is incorporated in an amount of from 0.5 to 10 parts by weight.
  • the resin composition of the present invention is useful for fiber reinforced plastics.
  • the reinforcing fibers may be glass fibers, carbon fibers, aramide fibers, alumina fibers or boron fibers. It is particularly preferred to employ carbon fibers having a high modulus of elasticity.
  • Such fiber reinforced plastics may be prepared by usual methods such as a solution method or a heat melting method.
  • a nitrile rubber-modifies epoxy resin obtained by preliminarily mixing and reacting 5 parts by weight of nitrile rubber (acrylonitrile content: 27%) and 95 parts by weight of a bisphenyl A type epoxy compound having an epoxy equivalent of 190 and being liquid at room temperature, 8 parts by weight of the above liquid epoxy compound (component A), 7 parts by weight of a solid epoxy compound having an epoxy equivalent of 460 and a melting point of 68°C (component B), 5 parts by weight of a solid epoxy compound having an epoxy equivalent of 3,000 and a melting point of 148°C (component C), 36 parts by weight of a phenol novolak type epoxy compound (component D), 4 parts by weight of an alicyclic epoxy compound (epoxy equivalent: 140, liquid at room temperature), 4 parts by weight of dicyandiamide as a curing agent (component F) and 3 parts by weight of N-(3,4-dichlorophenyl)-N',N'-
  • the viscosity of this composition was 20,000 poise at 40°C and 120 poise at 80°C.
  • a resin composition was prepared by uniformly mixing 46 parts by weight of component E, 8 parts by weight of component A, 6 parts by weight of component C, 40 parts by weight of component D, 4 parts by weight of the alicyclic epoxy compound, 3.5 parts by weight of dicyandiamide and 3.8 parts by weight of the curing accelerator.
  • the viscosity at 40°C of this resin composition was 6,000 poise.
  • a one-directional prepreg prepared by using this resin composition was wound on the mandrel as in Example 1, whereby the end portion of the winding was partially peeled.
  • a resin composition was prepared by uniformly mixing 40 parts by weight of component E, 8 parts by weight of component A, 12 parts by weight of component B, 40 parts by weight of component D, 4 parts by weight of the alicyclic epoxy compound, 3.5 parts by weight of component F and 3.8 parts by weight of the curing accelerator.
  • the viscosity at 40°C of this resin composition was 8,000 poise.
  • a one-directional prepreg prepared by using this resin composition was wound on the mandrel in the same manner as Example 1, whereby the end portion of the winding was partially peeled as in the case of Comparative Example 2.
  • a resin composition was prepared by uniformly mixing 27 parts by weight of component E, 8 parts by weight of component A, 25 parts by weight of component B, 40 parts by weight of component D, 4 parts by weight of the alicyclic epoxy compound, 3.5 parts by weight of component F and 3.8 parts by weight of the curing accelerator.
  • the viscosity of this resin composition was 22,000 poise at 40°C and 100 poise at 80°C.
  • a one-directional prepreg prepared by using this resin composition was wound on the mandrel in the same manner as in Example 1 and cured, whereby the prepreg lacked in flexibility and was poor to follow the shape of the mandrel. After the curing, the cross section was inspected, whereby breakage of fibers was observed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

An epoxy resin composition for fiber reinforced plastic comprising the following components A, B, C, D, E and F as essential components and having a viscosity at 40°C of at least 10,000 poise and a viscosity at 80°C of at most 200 poise:
  • A: a bisphenol A type epoxy compound having an epoxy equivalent of at most 250 and being liquid at room temperature,
  • B: a bisphenol A type epoxy compound having an epoxy equivalent of at most 1,000 and a softening point of at most 100°C and being solid at room temperature,
  • C: a bisphenol A type epoxy compound having an epoxy equivalent of at least 1,100 and a softening point of at least 110°C and being solid at room temperature,
  • D: a phenol novolak type epoxy compound,
  • E: a nitrile rubber, and
  • F: a curing agent.

Description

  • The present invention relates to a resin composition for fiber reinforced plastic. More particularly, it relates to a resin composition suitable for fiber reinforced plastic materials wherein fibers of high elasticity are employed.
  • It is well known to impregnate an epoxy resin or an unsaturated polyester resin to a reinforcing material such as carbon fibers or glass fibers, followed by curing to form molded products having various shapes and thicknesses. This method is now being used for the production of cylindrical molded products or shafts for sporting goods or primary or secondary structural materials for aircrafts, or for the production of various materials. The reinforcing material having a resin impregnated and serving as a matrix, is called prepreg and may be in the form of strands, sheets stretched in one direction or fabrics. To obtain a molded product having a desired shape, it is known to use a filament winding method which comprises winding prepreg strands, or a lay-up method which comprises laminating prepreg sheets.
  • To laminate prepreg sheets, it is important that the prepreg has a proper adhesiveness (tackiness) so that prepreg sheets adhere to one another at the time of laying up, and a flexibility (draping properties) so that laid up prepreg layers accurately reflect the shape such as a curved surface or cylinder. Under these circumstances, epoxy resin compositions having suitable tackiness and draping properties were proposed in Japanese Examined Patent Publications No. 5925/1983, No. 17535/1983 and No. 40975/1983 and Japanese Unexamined Patent Publications No. 43615/1986 and No. 127317/1987.
  • However, such conventional resin compositions had drawbacks that depending upon the shape or various properties such as mechanical and physical properties of the reinforcing material to be used, the operation efficiency depending upon the tackiness and draping properties substantially decreases, and consequently the operation tends to be cumbersome, or it is difficult to obtain a molded product having satisfactory properties. Under such circumstances, the present inventors have previously found that by a combination of resins having specific physical properties, it is possible to obtain a prepreg having excellent draping properties (Japanese Unexamined Patent Publication No. 308026/1988), and further found a resin composition for improving the strength in the direction of 90°C when a on directional prepreg is prepared (Japanese Patent Application No. 40517/1988). They have further found that by blending a phenol novolak type epoxy resin to such as resin composition, a molded product having no internal voids after the thermosetting molding can be obtained while adequately maintaining the shape-maintaining strength of the prepreg sheets and excellent draping properties (Japanese Patent Application No. 170228/1988).
  • Such a resin composition does not create any particular problem when applied to fiber reinforced plastic materials wherein reinforcing fibers of usual physical properties are employed. However, in a case where the reinforcing fibers have a high modulus of elasticity, the tackiness tends to be slightly poor, and it frequently happens that the shape after the shape-forming can not be maintained.
  • Under the circumstances, the present inventors have conducted extensive researchs to solve such a problem and as a result have found that the tackiness can be improved by using a combination of two bisphenol A type epoxy resins having specific physical properties and being solid at room temperature, as the high molecular weight components, whereby the conventional problems can be solved, and a resin composition having balanced properties can be obtained. The present invention has been accomplished on the basis of this discovery.
  • Namely, it is an object of the present invention to provide a resin composition which is excellent in the operation efficiency while maintaining excellent draping properties and the shape-maintaining strength of prepreg sheets and is capable of presenting a molded product having no voids in the interior of the molded product after thermosetting molding and which is most suitable for fiber reinforced plastic materials wherein reinforcing fibers of high modulus of elasticity are employed.
  • Such an object can be accomplished by an epoxy resin composition for fiber reinforced plastic comprising the following components A, B, C, D, E and F as essential components and having a viscosity at 40°C of at least 10,000 poise and a viscosity at 80°C of at most 200 poise:
    • A: a bisphenol A type epoxy compound having an epoxy equivalent of at most 250 and being liquid at room temperature,
    • B: a bisphenol A type epoxy compound having an epoxy equivalent of at most 1,000 and a softening point of at most 100°C and being solid at room temperature,
    • C: a bisphenol A type epoxy compound having an epoxy equivalent of at least 1,100 and a softening point of at least 110°C and being solid at room temperature,
    • D: a phenol novolak type epoxy compound,
    • E: a nitrile rubber, and
    • F: a curing agent.
  • Now, the present invention will be described in detail.
  • With respect to the bisphenol A type epoxy compound (component A) having an epoxy equivalent of at most 250 and being liquid at room temperature to be used in the present invention, there is no particular restriction so long as it has an epoxy equivalent of at most 250, preferably from 180 to 200 and it is liquid at room temperature. Specifically, the following compounds may be mentioned:
    "EPIKOTE" 816, 827, 828, manufactured by Yuka Shell Epoxy company,
    "Araldite" GY250, GY260, manufactured by Ciba Geigy Company,
    "AER" 334, 330, 331, manufactured by Asahi Chemical Industry Co., Ltd.,
    "Sumiepoxy" ELA-115, ELA-127, ELA-128, manufactured by Sumitomo Chemical Co., Ltd.,
    "EPICLON" 855, 840, 850, manufactured by Dai Nippon Ink Kagaku K.K.,
    "EPOTOHTO" YD-115, YD-127, YD-128, manufactured by TOHTO KASEI CO., LTD.,
    "EPOMIK" R130, R139, R140, manufactured by Mitsui Petrochemical Industries, Ltd.
  • With respect to the bisphenol A type epoxy compound (component B) having an epoxy equivalent of at most 1,000 and a softening point of at most 100°C and being solid at room temperature, any such compound may be used so long as it has an epoxy equivalent of at most 1,000, preferably from 400 to 1,000, and a softening point of at most 100°C, preferably from 60 to 100°C. Specifically, the following compounds may be mentioned:
    "EPOKOTE" 1001, 1002, 1004, manufactured by Yuka Shell Epoxy Company,
    "D. E. R." 661, 662, 664, manufactured by Daw Chemical Company,
    "Araldite" 6071, 7072, manufactured by Ciba Geigy Company,
    "Sumiepoxy" ESA-011, ESA=014, manufactured by Sumitomo Chemical Co., Ltd.,
    "EPOTOHTO" 1050, 4050, manufactured by Dai Nippon Ink Kagaku K.K.,
    "EPOTOHTO" YD-011, YD-127, YD-012, YD-014, manufactured by TOHTO KASEI CO., LTD.,
    "EPOMIK" R301, R302, R304, manufactured by Mitsui Petrochemical Industries, Ltd.
  • With respect to the bisphenol A type epoxy compound (component C) having an epoxy equivalent of at least 1,100 and a softening point of at least 110°C and being solid at room temperature, any such compound may be used so long as it has an epoxy equivalent of at least 1,100, preferably from 1,100 to 5,000, more preferably from 1,100 to 3,500, and a softening point of at least 110°C, preferably from 110 to 200°C, more preferably from 110 to 160°C. Specifically, the following compounds may be mentioned:
    "EPIKOTE" 1007, 1009, 1010, manufactured by Yuka Shell Epoxy Company,
    "D. E. R." 667, 668, 669, manufactured by Dow Chemical Company,
    "Araldite" 6097, 6099, manufactured by Ciba Geigy Company,
    "Sumiepoxy" ESA-017, ESA-019, manufactured by Sumitomo Chemical Co., Ltd.,
    "EPICLON" 7075, 7055, 9050, manufactured by Dai Nippon Ink Kagaku K.K.,
    "EPOTOHTO" YD-017, YD-119, manufactured by TOHTO KASEI CO., LTD.,
    "EPOMIK" R307, R309, manufactured by Mitsui Petrochemical Industries, Ltd.
  • The phenol novolak type epoxy compound (component D) means a compound of the formula:
    Figure imgb0001
    wherein n is an integer.
  • As such a phenol novolak type epoxy resin (component D), the following compounds may specifically be mentioned:
    "EPIKOTE" 152, 154, manufactured by Yuka Shell Epoxy Company,
    "Araldite" EPN1138, EPN1139, manufactured by Ciba Geigy Company,
    "D.E.N" 431, 438, 439, 485, manufactured by Daw Chemical Company,
    "EPPN" 201, manufactured by Nippon Kayaku K.K.,
    "EPICRON" N-730, N-738, N-740, manufactured by Dai Nippon Ink Kagaku K.K.
  • These compounds may be used alone or in combination as a mixture of two or more different types.
  • The nitrile rubber of component E is not particularly restricted, and it is usual to employ the one having an average molecular weight of at least 10,000. Specifically, a copolymer of butadiene and acrylonitrile may be employed. Further, it may be a copolymer having acrylic acid added to butadiene and acrylonitrile. It is usual to employ such copolymer having an average molecular weight of about 50,000. The acrylonitrile content is usually from 15 to 40% by weight.
  • The nitrile rubber of component E may be incorporated independently in the form of nitrile rubber to the epoxy resin composition of the present invention. However, it is preferred to preliminarily mixing and reacting it with the epoxy compound of component A so that it may be incorporated in the form of a nitrile rubber-modified epoxy compound thus obtained.
  • In the present invention, the above mentioned respective components are essential components, and their proportions are preferably such that relative to 100 parts by weight of component A, component B is from 5 to 40 parts by weight, component C is from 5 to 40 parts by weight, component D is from 50 to 140 parts by weight and component E is from 1 to 8 parts by weight. Further, it is important that the resin composition of the present invention has a viscosity at 40°C (η40°C) of at least 10,000 poise, preferably from 10,000 to 40,000 poise, more preferably from 10,000 to 30,000 poise and a viscosity at 80°C (η80°C) of at most 200 poise, preferably from 20 to 200 poise, more preferably from 50 to 150 poise.
  • If the viscosity (η40°C) is less than 10,000 poise, the surface tends to be sticky although the operation efficiency may be improved. On the other hand, if it is too high, the operation efficiency tends to be poor, since the hardness tends to be too high.
  • If the viscosity (η80°C) exceeds 200 poise, the moldability in heat molding tends to be poor. On the other hand, if the viscosity is too low, the flowability tends to be so excellent that the operation efficiency tends to be poor, such being undesirable.
  • Here, in the present invention, component A and components B and C primarily serve to adjust the viscosity of the resin composition. Particularly, in the present invention, the adhesive properties of the resin composition can be improved by the combined use of components B and C. Component E serves primarily to impart excellent operation efficiency and is effective particularly for the improvement of the flexibility of the resin composition.
  • Component D serves to prevent formation of voids in the interior of the molded product. If components D and E are not incorporated, it tends to be difficult to impart good flexibility with a proper viscosity during the preparation of prepreg sheets or during the molding operation, and voids tend to form in the interior of the molded product, such being very inconvenient.
  • As far as the physical properties of the resin mixture can be maintained, other components such as an aliphatic epoxy resin, an o-cresol novolak type epoxy resin, a polyglycidyl amine, a bisphenol F type epoxy resin, a brominated bisphenol A type epoxy resin, 1,1,2,2-tetrabis(4-glycidoxyphenyl)ethane, a glycidyl ester type epoxy resin and a monofunctional epoxy compound, may further be incorporated, as the case requires.
  • The curing agent of component F may usually be any curing agent. It may be dicyandiamide, an acid anhydride, an aromatic diamine, dimercaptan or a phenol resin. Further, in order to impart storage stability and low temperature curability to the prepreg, it is effective to employ a combination of dicyandiamide and a curing accelerator. Even when dicyandiamide is used alone, no change is required in the operation prior to the molding, provided that the molding compositions such as the curing temperature may vary. The curing accelerator may be an imidazole derivative such as 2-ethyl-4-methylimidazole or 2-(2-cyanoethyl)-imidazole, or a urea derivative such as N-(3,4-dichlorophenyl)-N',N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethylurea or N-(3-chlorophenyl)-N',N'-dimethylurea. In such a combination of curing agents i.e. a combination of dicyandiamide and a curing accelerator, it is preferred that dicyandiamine is incorporated in an amount of form 0.5 to 10 parts by weight, based on 100 parts by weight of the entire resin mixture, and the curing accelerator is incorporated in an amount of from 0.5 to 10 parts by weight.
  • The resin composition of the present invention is useful for fiber reinforced plastics. The reinforcing fibers may be glass fibers, carbon fibers, aramide fibers, alumina fibers or boron fibers. It is particularly preferred to employ carbon fibers having a high modulus of elasticity. Such fiber reinforced plastics may be prepared by usual methods such as a solution method or a heat melting method.
  • Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted to such specific Examples.
    • Example 1
  • 33 parts by weight of a nitrile rubber-modifies epoxy resin (component E) obtained by preliminarily mixing and reacting 5 parts by weight of nitrile rubber (acrylonitrile content: 27%) and 95 parts by weight of a bisphenyl A type epoxy compound having an epoxy equivalent of 190 and being liquid at room temperature, 8 parts by weight of the above liquid epoxy compound (component A), 7 parts by weight of a solid epoxy compound having an epoxy equivalent of 460 and a melting point of 68°C (component B), 5 parts by weight of a solid epoxy compound having an epoxy equivalent of 3,000 and a melting point of 148°C (component C), 36 parts by weight of a phenol novolak type epoxy compound (component D), 4 parts by weight of an alicyclic epoxy compound (epoxy equivalent: 140, liquid at room temperature), 4 parts by weight of dicyandiamide as a curing agent (component F) and 3 parts by weight of N-(3,4-dichlorophenyl)-N',N'-dimethylurea as a curing accelerator, were uniformly mixed under heating to obtain a resin composition of the present invention. The viscosity of this composition was 20,000 poise at 40°C and 120 poise at 80°C. A one-directional prepreg obtained, from this resin composition and highly elastic carbon fibers having a modulus of elasticity of 65,000 kg/mm², was wound on a slightly tapered cylindrical mandrel having a diameter of 10 mℓ at an angle of 45°, whereby lamination reflecting the shape of the mandrel was possible, and the operation efficiency was excellent. Further, no defects such as voids were observed in the molded products after curing.
    • Comparative Example 1
  • In the same manner as in Example 1, a resin composition was prepared by uniformly mixing 46 parts by weight of component E, 8 parts by weight of component A, 6 parts by weight of component C, 40 parts by weight of component D, 4 parts by weight of the alicyclic epoxy compound, 3.5 parts by weight of dicyandiamide and 3.8 parts by weight of the curing accelerator. The viscosity at 40°C of this resin composition was 6,000 poise. A one-directional prepreg prepared by using this resin composition was wound on the mandrel as in Example 1, whereby the end portion of the winding was partially peeled.
    • Comparative Example 2
  • In the same manner as in Example 1, a resin composition was prepared by uniformly mixing 40 parts by weight of component E, 8 parts by weight of component A, 12 parts by weight of component B, 40 parts by weight of component D, 4 parts by weight of the alicyclic epoxy compound, 3.5 parts by weight of component F and 3.8 parts by weight of the curing accelerator. The viscosity at 40°C of this resin composition was 8,000 poise. A one-directional prepreg prepared by using this resin composition was wound on the mandrel in the same manner as Example 1, whereby the end portion of the winding was partially peeled as in the case of Comparative Example 2.
    • Comparative Example 3
  • In the same manner as in Example 1, a resin composition was prepared by uniformly mixing 27 parts by weight of component E, 8 parts by weight of component A, 25 parts by weight of component B, 40 parts by weight of component D, 4 parts by weight of the alicyclic epoxy compound, 3.5 parts by weight of component F and 3.8 parts by weight of the curing accelerator. The viscosity of this resin composition was 22,000 poise at 40°C and 100 poise at 80°C. A one-directional prepreg prepared by using this resin composition was wound on the mandrel in the same manner as in Example 1 and cured, whereby the prepreg lacked in flexibility and was poor to follow the shape of the mandrel. After the curing, the cross section was inspected, whereby breakage of fibers was observed.
    Figure imgb0002
  • According to the present invention, it is possible to obtain a resin composition for fiber reinforced plastic which is excellent in the operation efficiency and which is capable of presenting a flawless molded product.

Claims (9)

  1. An epoxy resin composition for fiber reinforced plastic comprising the following components A, B, C, D, E and F as essential components and having a viscosity at 40°C of at least 10,000 poise and a viscosity at 80°C of at most 200 poise:
    A: a bisphenol A type epoxy compound having an epoxy equivalent of at most 250 and being liquid at room temperature,
    B: a bisphenol A type epoxy compound having an epoxy equivalent of at most 1,000 and a softening point of at most 100°C and being solid at room temperature,
    C: a bisphenol A type epoxy compound having an epoxy equivalent of at least 1,100 and a softening point of at least 110°C and being solid at room temperature,
    D: a phenol novolak type epoxy compound,
    E: a nitrile rubber, and
    F: a curing agent.
  2. The epoxy resin composition according to Claim 1, wherein relative to 100 parts by weight of component A, component B is from 5 to 40 parts by weight, component C is from 5 to 40 parts by weight, component D is from 50 to 140 parts by weight, and component E is from 1 to 8 parts by weight.
  3. The epoxy resin composition according to Claim 1 or 2, wherein the epoxy equivalent of component A is from 180 to 200.
  4. The epoxy resin composition according to Claim 1, 2 or 3 wherein the epoxy equivalent of component B from 400 to 1,000.
  5. The epoxy resin composition according to any of Claims 1 to 4, wherein the softening point of component B is from 60 to 100°C.
  6. The epoxy resin composition according to any one of Claims 1 to 5, wherein the epoxy equivalent of component C is from 1,100 to 5,000.
  7. The epoxy resin composition according to any one of Claims 1 to 6, wherein epoxy equivalent of component C is from 1,100 to 3,500.
  8. The epoxy resin composition according to any one of Claims 1 to 7, wherein the softening point of component C is from 110 to 200°C.
  9. The epoxy resin composition according to any one of Claims 1 to 8, wherein the average molecular weight of component E is at least 10,000.
EP90125692A 1990-01-08 1990-12-28 Epoxy resin composition for fiber reinforced plastic Expired - Lifetime EP0436944B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1174/90 1990-01-08
JP2001174A JPH03205420A (en) 1990-01-08 1990-01-08 Epoxy resin composition for fiber reinforced plastics

Publications (3)

Publication Number Publication Date
EP0436944A2 true EP0436944A2 (en) 1991-07-17
EP0436944A3 EP0436944A3 (en) 1992-04-22
EP0436944B1 EP0436944B1 (en) 1995-10-11

Family

ID=11494075

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90125692A Expired - Lifetime EP0436944B1 (en) 1990-01-08 1990-12-28 Epoxy resin composition for fiber reinforced plastic

Country Status (5)

Country Link
US (1) US5302666A (en)
EP (1) EP0436944B1 (en)
JP (1) JPH03205420A (en)
KR (1) KR0166977B1 (en)
DE (1) DE69022966T2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545640A1 (en) * 1991-11-29 1993-06-09 Tonen Corporation Epoxy resin composition, prepreg containing same and process for the producing of prepreg using same
WO2000050495A1 (en) * 1999-02-22 2000-08-31 Toray Industries, Inc. Prepreg and fiber-reinforced rubber materials
GB2517554A (en) * 2013-06-19 2015-02-25 Hexcel Composites Ltd Improvements in or relating to epoxy resin formulations
EP3157982A4 (en) * 2014-06-23 2018-01-17 Ut-battelle, Llc Polymer blend compositions and methods of preparation

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9411367D0 (en) 1994-06-07 1994-07-27 Ici Composites Inc Curable Composites
US5976699A (en) * 1995-11-09 1999-11-02 Sumitomo Bakelite Company Limited Insulating adhesive for multilayer printed circuit board
KR100576767B1 (en) * 1998-05-20 2006-05-09 사이텍 테크놀러지 코포레이션 Method for producing a non-porous laminate and its use
US6322848B1 (en) * 1999-10-26 2001-11-27 Lord Corporation Flexible epoxy encapsulating material
US20050026069A1 (en) * 2003-07-31 2005-02-03 Todd Yeh Solventless thermosetting photosensitive via-filling material
JP4553595B2 (en) * 2004-01-29 2010-09-29 株式会社有沢製作所 Prepreg resin composition and prepreg using the same
DE102005026191A1 (en) * 2005-06-06 2006-12-07 Tesa Ag Heat-activatable films for fixing metal parts on plastics
CN101501132A (en) * 2006-06-30 2009-08-05 东丽株式会社 Epoxy resin composition, prepreg, and fiber-reinforced composite material
JP5150381B2 (en) * 2008-06-20 2013-02-20 太陽ホールディングス株式会社 Thermosetting resin composition
DE102013201958A1 (en) * 2013-02-06 2014-08-07 Vacuumschmelze Gmbh & Co. Kg Composition for an adhesive composition
US9815985B2 (en) 2015-07-14 2017-11-14 Ut-Battelle, Llc High performance lignin-acrylonitrile polymer blend materials
KR101714191B1 (en) * 2015-08-12 2017-03-08 현대자동차주식회사 Polyphenylene ether flame retardant resin composition having high rigidity and impact strength
US11124652B2 (en) 2017-06-21 2021-09-21 Ut-Battelle, Llc Shape memory polymer blend materials
CN109762302A (en) * 2019-02-15 2019-05-17 无锡市立帆绝缘材料科技有限公司 Prepreg and preparation method thereof for glass grid cloth
CN111944274A (en) * 2020-08-05 2020-11-17 华烁科技股份有限公司 Bendable prepreg gumming solution for circuit board, prepreg and preparation method of prepreg

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2525617A1 (en) * 1982-04-21 1983-10-28 Toho Beslon Co EPOXY RESIN COMPOSITION
JPS6143615A (en) * 1984-08-07 1986-03-03 Mitsui Petrochem Ind Ltd Epoxy resin composition
JPH01215850A (en) * 1988-02-23 1989-08-29 Mitsubishi Kasei Corp Resin composition for fiber reinforced plastics
JPH0220546A (en) * 1988-07-08 1990-01-24 Mitsubishi Kasei Corp Resin composition for fiber-reinforced plastics

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894113A (en) * 1966-09-15 1975-07-08 Minnesota Mining & Mfg Bonding film
US3707583A (en) * 1971-06-04 1972-12-26 Minnesota Mining & Mfg Adhesive
US3948849A (en) * 1974-11-01 1976-04-06 Gulf Research & Development Company Adhesive compositions
US4040993A (en) * 1976-02-25 1977-08-09 Westinghouse Electric Corporation Low dissipation factor electrostatic epoxy wire coating powder
EP0032062B2 (en) * 1979-12-27 1991-10-16 Mitsui Petrochemical Industries, Ltd. High-molecular-weight novolak substituted phenolic resins and their preparation
JPS6340517A (en) * 1986-08-07 1988-02-20 松下電器産業株式会社 Electric cooker
JPS63170228A (en) * 1987-01-08 1988-07-14 Toshiba Mach Co Ltd Press-molding device for glass lens
US5143950A (en) * 1987-02-07 1992-09-01 Somar Corporation Power coating of epoxy resin mixture and polyvinyl butyral or formal resin
JPS63308026A (en) * 1987-06-09 1988-12-15 Mitsubishi Kasei Corp Polymer composition for fiber-reinforced plastic
US4798761A (en) * 1987-11-03 1989-01-17 The Dow Chemical Company Epoxy resin compositions for use in low temperature curing applications
JPH01185351A (en) * 1988-01-18 1989-07-24 Nissan Motor Co Ltd Epoxy resin composition for carbon fiber reinforced material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2525617A1 (en) * 1982-04-21 1983-10-28 Toho Beslon Co EPOXY RESIN COMPOSITION
JPS6143615A (en) * 1984-08-07 1986-03-03 Mitsui Petrochem Ind Ltd Epoxy resin composition
JPH01215850A (en) * 1988-02-23 1989-08-29 Mitsubishi Kasei Corp Resin composition for fiber reinforced plastics
JPH0220546A (en) * 1988-07-08 1990-01-24 Mitsubishi Kasei Corp Resin composition for fiber-reinforced plastics

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 10, no. 203 (C-360)(2259) 16 July 1986 & JP-A-61 043 615 ( MITSUI PETROCHEM IND LTD ) 3 March 1986 *
PATENT ABSTRACTS OF JAPAN vol. 13, no. 529 (C-658)(3877) 27 November 1989 & JP-A-1 215 850 ( MITSUBISHI KASEI CORP. ) 29 August 1989 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 149 (C-705)(4092) 22 March 1990 & JP-A-2 020 546 ( MITSUBISHI KASEI CORP. ) 24 January 1990 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0545640A1 (en) * 1991-11-29 1993-06-09 Tonen Corporation Epoxy resin composition, prepreg containing same and process for the producing of prepreg using same
US5350826A (en) * 1991-11-29 1994-09-27 Tonen Corporation Epoxy resin composition containing a polyaminoamide and a latent curing agent for fiber impregnation
WO2000050495A1 (en) * 1999-02-22 2000-08-31 Toray Industries, Inc. Prepreg and fiber-reinforced rubber materials
GB2517554A (en) * 2013-06-19 2015-02-25 Hexcel Composites Ltd Improvements in or relating to epoxy resin formulations
GB2517554B (en) * 2013-06-19 2016-06-29 Hexcel Composites Ltd Improvements in or relating to epoxy resin formulations
EP3157982A4 (en) * 2014-06-23 2018-01-17 Ut-battelle, Llc Polymer blend compositions and methods of preparation

Also Published As

Publication number Publication date
EP0436944B1 (en) 1995-10-11
KR910021444A (en) 1991-12-20
DE69022966D1 (en) 1995-11-16
DE69022966T2 (en) 1996-06-20
JPH03205420A (en) 1991-09-06
EP0436944A3 (en) 1992-04-22
KR0166977B1 (en) 1999-03-20
US5302666A (en) 1994-04-12

Similar Documents

Publication Publication Date Title
EP0436944B1 (en) Epoxy resin composition for fiber reinforced plastic
KR100623457B1 (en) Resin Compositions, Prepregs and Fiber Reinforced Composites for Fiber Reinforced Composites
US6063839A (en) Prepreg of reinforcing fibers, epoxy resins, crosslinked rubber particles and curing agent
EP0259100B1 (en) Multiphase epoxy thermosets having rubber within disperse phase
CN102666638B (en) composite material composition
WO1992011307A1 (en) Latent, heat-curable epoxy resin compositions containing metal carboxylate curing systems
EP0583224B1 (en) Thermosetting resins toughened with sulfone polymers
JP3796953B2 (en) Resin composition for fiber reinforced composite material, prepreg and fiber reinforced composite material
WO2019167579A1 (en) Heat-curable resin composition, prepreg, and fiber-reinforced composite material
JPH11172076A (en) Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material
EP0493786B1 (en) Resin composition and process for producing the composition
JPS61188413A (en) epoxy resin composition
US5225486A (en) Epoxy resins containing epoxidized polybutenes
JP3097259B2 (en) Epoxy resin composition and prepreg
US5128425A (en) Epoxy resin composition for use in carbon fiber reinforced plastics, containing amine or amide based fortifiers
JPH11279261A (en) Heat-resistant epoxy resin composition for fiber-reinforced composite material
JP2004027043A (en) Epoxy resin composition for fiber-reinforced composite material and the resulting fiber-reinforced composite material
JPH0717734B2 (en) Resin composition for fiber reinforced plastic
JP2650302B2 (en) Resin composition for fiber reinforced plastic
JP3354707B2 (en) Epoxy resin composition
JPH0586425B2 (en)
JPS6360056B2 (en)
JP3314813B2 (en) Epoxy resin composition for laminate and laminate using the same
JP3867377B2 (en) Epoxy resin composition for fiber reinforced composite material, prepreg and fiber reinforced composite material
JPS6338048B2 (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901228

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB

17Q First examination report despatched

Effective date: 19941212

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: MITSUBISHI CHEMICAL CORPORATION

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 69022966

Country of ref document: DE

Date of ref document: 19951116

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19991124

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19991126

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19991231

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001228

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20001228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011002